12.4: Petroleum

Petroleum is a naturally occurring, yellow-to-black liquid found in geological formations beneath the Earth’s surface, which is commonly refined into various types of fuels.

Figure 1. Pumpjack pumping an oil well near Lubbock, Texas

It consists of hydrocarbons of various molecular weights and other organic compounds. The name petroleum covers both naturally occurring unprocessed crude oil and petroleum products that are made up of refined crude oil. A fossil fuel, petroleum is formed when large quantities of dead organisms, usually zooplankton and algae, are buried underneath sedimentary rock and subjected to intense heat and pressure.

Petroleum is recovered mostly through oil drilling (natural petroleum springs are rare). This comes after the studies of structural geology (at the reservoir scale), sedimentary basin analysis, reservoir characterization (mainly in terms of the porosity and permeability of geologic reservoir structures). It is refined and separated, most easily by distillation, into a large number of consumer products, from gasoline (petrol) and kerosene to asphalt and chemical reagents used to make plastics and pharmaceuticals. Petroleum is used in manufacturing a wide variety of materials, and it is estimated that the world consumes about 90 million barrels each day.

Concern over the depletion of the earth’s finite reserves of oil, and the effect this would have on a society dependent on it, is a concept known as peak oil. The use of fossil fuels, such as petroleum, has a negative impact on Earth’s biosphere, damaging ecosystems through events such as oil spills and releasing a range of pollutants into the air including ground-level ozone and sulfur dioxide from sulfur impurities in fossil fuels.

COMPOSITION

In its strictest sense, petroleum includes only crude oil, but in common usage it includes all liquid, gaseous, and solid hydrocarbons. Under surface pressure and temperature conditions, lighter hydrocarbons methane, ethane, propane and butane occur as gases, while pentane and heavier ones are in the form of liquids or solids. However, in an underground oil reservoir the proportions of gas, liquid, and solid depend on subsurface conditions and on the phase diagram of the petroleum mixture.

An oil well produces predominantly crude oil, with some natural gas dissolved in it. Because the pressure is lower at the surface than underground, some of the gas will come out of solution and be recovered (or burned) as associated gas or solution gas. A gas well produces predominantly natural gas. However, because the underground temperature and pressure are higher than at the surface, the gas may contain heavier hydrocarbons such as pentane, hexane, and heptane in the gaseous state. At surface conditions these will condense out of the gas to form natural gas condensate, often shortened to condensate. Condensate resembles gasoline in appearance and is similar in composition to some volatile light crude oils.

The proportion of light hydrocarbons in the petroleum mixture varies greatly among different oil fields, ranging from as much as 97 percent by weight in the lighter oils to as little as 50 percent in the heavier oils and bitumens.

The hydrocarbons in crude oil are mostly alkanes, cycloalkanes and various aromatic hydrocarbons while the other organic compounds contain nitrogen, oxygen and sulfur, and trace amounts of metals such as iron, nickel, copper and vanadium. Many oil reservoirs contain live bacteria. The exact molecular composition varies widely from formation to formation but the proportion of chemical elements vary over fairly narrow limits as follows:

Composition by weight

Element	Percent range
Carbon	83 to 85%
Hydrogen	10 to 14%
Nitrogen	0.1 to 2%
Oxygen	0.05 to 1.5%
Sulfur	0.05 to 6.0%
Metals	< 0.1%

Four different types of hydrocarbon molecules appear in crude oil. The relative percentage of each varies from oil to oil, determining the properties of each oil.

Composition by weight

Hydrocarbon	Average	Range
Alkanes (paraffins)	30%	15 to 60%
Naphthenes	49%	30 to 60%
Aromatics	15%	3 to 30%
Asphaltics	6%	remainder

Crude oil varies greatly in appearance depending on its composition. It is usually black or dark brown (although it may be yellowish, reddish, or even greenish). In the reservoir it is usually found in association with natural gas, which being lighter forms a gas cap over the petroleum, and saline water which, being heavier than most forms of crude oil, generally sinks beneath it. Crude oil may also be found in semi-solid form mixed with sand and water, as in the Athabasca oil sands in Canada, where it is usually referred to as crude bitumen. In Canada, bitumen is considered a sticky, black, tar-like form of crude oil which is so thick and heavy that it must be heated or diluted before it will flow. Venezuela also has large amounts of oil in the Orinoco oil sands, although the hydrocarbons trapped in them are more fluid than in Canada and are usually called extra heavy oil. These oil sands resources are called unconventional oil to distinguish them from oil which can be extracted using traditional oil well methods. Between them, Canada and Venezuela contain an estimated 3.6 trillion barrels (570×10⁹ m³) of bitumen and extra-heavy oil, about twice the volume of the world’s reserves of conventional oil.

Petroleum is used mostly, by volume, for producing fuel oil and gasoline, both important “primary energy” sources. 84 percent by volume of the hydrocarbons present in petroleum is converted into energy-rich fuels (petroleum-based fuels), including gasoline, diesel, jet, heating, and other fuel oils, and liquefied petroleum gas. The lighter grades of crude oil produce the best yields of these products, but as the world’s reserves of light and medium oil are depleted, oil refineries are increasingly having to process heavy oil and bitumen, and use more complex and expensive methods to produce the products required. Because heavier crude oils have too much carbon and not enough hydrogen, these processes generally involve removing carbon from or adding hydrogen to the molecules, and using fluid catalytic cracking to convert the longer, more complex molecules in the oil to the shorter, simpler ones in the fuels.

Due to its high energy density, easy transportability and relative abundance, oil has become the world’s most important source of energy since the mid-1950s. Petroleum is also the raw material for many chemical products, including pharmaceuticals, solvents, fertilizers, pesticides, and plastics; the 16 percent not used for energy production is converted into these other materials. Petroleum is found in porous rock formations in the upper strata of some areas of the Earth’s crust. There is also petroleum in oil sands (tar sands). Known oil reserves are typically estimated at around 190 km³(1.2 trillion (short scale) barrels) without oil sands, or 595 km³ (3.74 trillion barrels) with oil sands. Consumption is currently around 84 million barrels (13.4×10⁶ m³) per day, or 4.9 km³ per year. Which in turn yields a remaining oil supply of only about 120 years, if current demand remain static.

FORMATION

Petroleum is a fossil fuel derived from ancient fossilized organic materials, such as zooplankton and algae. Vast quantities of these remains settled to sea or lake bottoms, mixing with sediments and being buried under anoxic conditions. As further layers settled to the sea or lake bed, intense heat and pressure build up in the lower regions. This process caused the organic matter to change, first into a waxy material known as kerogen, which is found in various oil shales around the world, and then with more heat into liquid and gaseous hydrocarbons via a process known as catagenesis. Formation of petroleum occurs from hydrocarbon pyrolysis in a variety of mainly endothermic reactions at high temperature and/or pressure.

Figure 2. Natural petroleum spring in Korňa, Slovakia

There were certain warm nutrient-rich environments such as the Gulf of Mexico and the ancient Tethys Sea where the large amounts of organic material falling to the ocean floor exceeded the rate at which it could decompose. This resulted in large masses of organic material being buried under subsequent deposits such as shale formed from mud. This massive organic deposit later became heated and transformed under pressure into oil.

Geologists often refer to the temperature range in which oil forms as an “oil window”—below the minimum temperature oil remains trapped in the form of kerogen, and above the maximum temperature the oil is converted to natural gas through the process of thermal cracking. Sometimes, oil formed at extreme depths may migrate and become trapped at a much shallower level. The Athabasca Oil Sands are one example of this.

An alternative mechanism was proposed by Russian scientists in the mid-1850s, the Abiogenic petroleum origin, but this is contradicted by the geological and geochemical evidence.

RESERVOIRS

Crude Oil Reservoirs

Three conditions must be present for oil reservoirs to form: a source rock rich in hydrocarbon material buried deep enough for subterranean heat to cook it into oil, a porous and permeable reservoir rock for it to accumulate in, and a cap rock (seal) or other mechanism that prevents it from escaping to the surface. Within these reservoirs, fluids will typically organize themselves like a three-layer cake with a layer of water below the oil layer and a layer of gas above it, although the different layers vary in size between reservoirs. Because most hydrocarbons are less dense than rock or water, they often migrate upward through adjacent rock layers until either reaching the surface or becoming trapped within porous rocks (known as reservoirs) by impermeable rocks above. However, the process is influenced by underground water flows, causing oil to migrate hundreds of kilometres horizontally or even short distances downward before becoming trapped in a reservoir. When hydrocarbons are concentrated in a trap, an oil field forms, from which the liquid can be extracted by drilling and pumping.

The reactions that produce oil and natural gas are often modeled as first order breakdown reactions, where hydrocarbons are broken down to oil and natural gas by a set of parallel reactions, and oil eventually breaks down to natural gas by another set of reactions. The latter set is regularly used in petrochemical plants and oil refineries.

Wells are drilled into oil reservoirs to extract the crude oil. “Natural lift” production methods that rely on the natural reservoir pressure to force the oil to the surface are usually sufficient for a while after reservoirs are first tapped. In some reservoirs, such as in the Middle East, the natural pressure is sufficient over a long time. The natural pressure in most reservoirs, however, eventually dissipates. Then the oil must be extracted using “artificial lift” means. Over time, these “primary” methods become less effective and “secondary” production methods may be used. A common secondary method is “waterflood” or injection of water into the reservoir to increase pressure and force the oil to the drilled shaft or “wellbore.” Eventually “tertiary” or “enhanced” oil recovery methods may be used to increase the oil’s flow characteristics by injecting steam, carbon dioxide and other gases or chemicals into the reservoir. In the United States, primary production methods account for less than 40 percent of the oil produced on a daily basis, secondary methods account for about half, and tertiary recovery the remaining 10 percent. Extracting oil (or “bitumen”) from oil/tar sand and oil shale deposits requires mining the sand or shale and heating it in a vessel or retort, or using “in-situ” methods of injecting heated liquids into the deposit and then pumping out the oil-saturated liquid.

Unconventional Oil Reservoirs

Oil-eating bacteria biodegrade oil that has escaped to the surface. Oil sands are reservoirs of partially biodegraded oil still in the process of escaping and being biodegraded, but they contain so much migrating oil that, although most of it has escaped, vast amounts are still present—more than can be found in conventional oil reservoirs. The lighter fractions of the crude oil are destroyed first, resulting in reservoirs containing an extremely heavy form of crude oil, called crude bitumen in Canada, or extra-heavy crude oil in Venezuela. These two countries have the world’s largest deposits of oil sands.

On the other hand, oil shales are source rocks that have not been exposed to heat or pressure long enough to convert their trapped hydrocarbons into crude oil. Technically speaking, oil shales are not always shales and do not contain oil, but are fined-grain sedimentary rocks containing an insoluble organic solid called kerogen. The kerogen in the rock can be converted into crude oil using heat and pressure to simulate natural processes. The method has been known for centuries and was patented in 1694 under British Crown Patent No. 330 covering, “A way to extract and make great quantities of pitch, tar, and oil out of a sort of stone.” Although oil shales are found in many countries, the United States has the world’s largest deposits.

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Contributors and Attributions

• Original content from Kimberly Schulte (Columbia Basin College) and supplemented by Lumen Learning. The content on this page is copyrighted under a Creative Commons Attribution 4.0 International license.